JP2007045906A - Flame-retardant polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant polycarbonate resin composition free from a halogen and excellent in balance aspect of heat resistance, impact strength, fluidity, light resistance, etc. <P>SOLUTION: The flame-retardant polycarbonate resin composition is composed of 100 pts.wt. resin component composed of (A) 1-99 wt.% polycarbonate resin and (B) 99-1 wt.% rubber-reinforced styrene-based resin, (C) 0.5-25 pts.wt. phosphazene compound, (D) 0-10 pts.wt. rubber-like elastomer, (E) 0.01-2 pts.wt. fiber-forming type fluorine-containing polymer, (F) 0.01-2 pts.wt. acid scavenger and (G) 0.01-3 pts.wt. mold-releasing agent. A molded article is obtained by molding the resin composition. Since the flame-retardant polycarbonate resin composition does not contain a halogen-based flame retardant composed of a chlorine or bromine compound, etc., the resin composition is excellent in the aspect of environmental protection and further has performances of high flame retardancy, mechanical physical properties, deterioration to moist heat and surface appearance, etc., and can suitably be used as a material for various interior and exterior applications in electrical/electronic applications and OA. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

 In the present invention, a blend of a polycarbonate resin and a rubber-reinforced styrene resin is blended with a specific phosphazene compound, a fluororesin as an anti-dripping agent, an acid scavenger, a release agent, and, if necessary, a rubber-like elastic body. The present invention relates to a flame retardant polycarbonate resin composition. The resin composition according to the present invention is excellent in flame retardancy, and further excellent in mechanical strength, moldability, wet heat degradation, surface appearance, etc., and thus particularly in various applications such as electric, electronic, and OA fields. Can be used widely.

  Polycarbonate resin is a thermoplastic resin excellent in impact resistance, heat resistance, and the like, and is widely used in fields such as electricity, electronics, OA, machinery, and automobiles. On the other hand, in addition to these excellent performances possessed by the polycarbonate resin, in order to satisfy safety requirements in fields such as electricity, electronics and OA, a material having high flame retardancy is required. Therefore, various methods of blending various flame retardants represented by organic bromine compounds and phosphorus compounds have been proposed and adopted in order to improve the flame retardancy of polycarbonate resins.

However, when a halogen-based compound such as an organic bromine compound is blended, there is a concern that a gas containing the halogen is generated during combustion, and the use of a flame retardant that does not contain chlorine, bromine, or the like is desired from the market. ing.

In addition, as a flame retardant polycarbonate resin, many resin compositions are disclosed in which a phosphorus flame retardant represented by a phosphoric ester is added as a non-halogen material. In particular, due to the problem of mold deposit at the time of molding, for example, resorcinol Publications using condensed phosphate esters having a structure derived from are published.

However, a polycarbonate resin composition containing a condensed phosphoric ester is not always satisfactory in terms of the balance of heat resistance, impact strength, fluidity, and light resistance.

JP 59-156738 A Japanese Patent Laid-Open No. 06-184357 JP 09-95610 A JP-A-11-130954

Under such circumstances, it has been desired to develop a flame retardant polycarbonate resin composition which does not contain halogen and has an excellent balance of heat resistance, impact strength, fluidity, light resistance and the like.

As a result of intensive studies to solve the above problems, the present inventor has found that a specific phosphazene compound, a fiber-forming fluorine-containing polymer, an acid scavenger, a mold release, for a blend of a polycarbonate resin and a rubber-reinforced styrene resin. The present inventors have found that a composition containing a specific amount of an agent and, if necessary, a rubber-like elastic body exhibits surprising flame retardancy and mechanical strength, and has completed the present invention.

That is, the present invention
0.5 to 25 parts by weight of the phosphazene compound (C), rubber-like elasticity with respect to 100 parts by weight of the composite composition of 1 to 99% by weight of the polycarbonate resin (A) and 99 to 1% by weight of the rubber-reinforced styrene resin (B) Body (D) 0 to 10 parts by weight, fiber-forming fluoropolymer (E) 0.01 to 2 parts by weight, acid scavenger (F) 0.01 to 2 parts by weight and release agent (G) 0.01 By adding 3 parts by weight, a flame-retardant polycarbonate resin composition having excellent flame retardancy, mechanical strength, moldability, wet heat degradation, surface appearance and other performances, and a molded product formed by molding the same Is to provide.

The flame-retardant polycarbonate resin composition of the present invention does not contain a halogen-based flame retardant composed of chlorine, bromine compounds, etc., so it is excellent in terms of environmental protection, and further has high flame resistance, mechanical properties, and wet heat degradation. Performance and surface appearance, and can be suitably used as a material for various interior and exterior applications in relation to electrical / electronic and OA.

The polycarbonate resin (A) used in the present invention is obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted. A typical example of the polymer is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) -Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 ' -Dihydroxy diaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxy diary such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Sulfone, and the like.

These are used singly or as a mixture of two or more. However, it is preferable not to be substituted with a halogen from the viewpoint of preventing discharge of a gas containing halogen, which is a concern during combustion, into the environment. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, and the like may be mixed and used.

  Furthermore, the above dihydroxyaryl compound and a trivalent or higher phenol compound as shown below may be used in combination. Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4 4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

  The viscosity average molecular weight of the polycarbonate resin (A) is usually 10,000 to 100,000, preferably 15,000 to 35,000, and more preferably 18000 to 23,000. In producing such an aromatic polycarbonate resin, a molecular weight regulator, a catalyst, and the like can be used as necessary.

The rubber-reinforced styrenic resin (B) used in the present invention includes (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component, and (c) a rubbery polymer. It is composed of (B-1) a copolymer containing as a constituent component of a coalescence and (B-2) a copolymer containing (a) and (b) as constituent components of the copolymer. Resin. Examples of the preferred rubber-reinforced styrene resin (B) include those containing (c) a graft copolymer obtained by graft copolymerization of the components (a) and (b) in the presence of a rubbery polymer, Preferably, ABS resin (acrylonitrile-butadiene-styrene copolymer) produced by bulk polymerization is used.

(A) Examples of the aromatic vinyl monomer component include styrene, α-methylstyrene, o-, m-, p-methylstyrene, vinylxylene, ethylstyrene, vinylnaphthalene, and the like. More than seeds can be used. Of these components, styrene is preferably used.

(B) As a vinyl cyanide monomer component, acrylonitrile, methacrylonitrile, etc. are mentioned, for example, These can be used 1 type, or 2 or more types. Of these components, acrylonitrile is preferably used.

(C) Examples of the rubbery polymer include polybutadiene, styrene-butadiene random copolymer or block copolymer, hydrogenated product of the block copolymer, acrylonitrile-butadiene copolymer, isoprene-butadiene copolymer, etc. Diene rubber, ethylene-propylene random copolymer or block copolymer, polyisoprene, ethylene and α-olefin copolymer, ethylene-unsaturated such as ethylene-methacrylate, ethylene-butyl acrylate Copolymers with carboxylates, acrylic ester-butadiene copolymers, acrylic elastic polymers such as butyl acrylate-butadiene copolymers, copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate , Ethylene-propylene-hexadiene copolymer, etc. Len - propylene nonconjugated Jienta - polymer -, butylene - Isoburen copolymers, chlorinated polyethylene and the like, may be to use them in one or two or more thereof. Preferred rubbery polymers are diene rubber, ethylene-propylene non-conjugated diene polymer, and acrylic elastic polymer, and polybutadiene and styrene-butadiene copolymers are preferably used.

There is no restriction | limiting in particular in the composition ratio of each component of said (a), (b), (c), It can adjust according to a use. In addition to the components (a), (b), and (c) described above, the copolymer (B-1) does not impair the purpose of the present invention. Can be used in a range.

Examples of such copolymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( Α, β-unsaturated carboxylic acid esters such as (meth) acrylate, 2-ethyl (meth) acrylate, 2-ethylhexyl methacrylate; α, β-unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; And imide compounds of α, β-unsaturated dicarboxylic acids such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-o-chlorophenylmaleimide, and the like. Can be used alone or in combination of two or more.

(B-2) The copolymer is composed of the above-mentioned (a) aromatic vinyl monomer component and (b) vinyl cyanide monomer component, preferably SAN resin (styrene-acrylonitrile copolymer). Is used. (B-2) A copolymer contributes to the improvement of the moldability (fluidity) of the obtained flame-retardant thermoplastic resin composition.

There is no restriction | limiting in particular in the composition ratio of each component of said (a), (b), Although it can adjust according to a use, Preferably, it is based on (B-2) copolymer (a) component Is 95 to 50% by weight, component (b) is 5 to 50% by weight, more preferably (a) is 90 to 65% by weight, and (b) is 10 to 35% by weight. In addition to the components (a) and (b), a monomer that can be copolymerized with these components is used in the copolymer (B-2) within a range that does not impair the object of the present invention. be able to.

Examples of such copolymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( Α, β-unsaturated carboxylic acid esters such as (meth) acrylate, 2-ethyl (meth) acrylate, 2-ethylhexyl methacrylate; α, β-unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; And imide compounds of α, β-unsaturated dicarboxylic acids such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-o-chlorophenylmaleimide, and the like. Can be used alone or in combination of two or more.

The phosphazene compound (C) used in the present invention is, for example, a linear phosphazene represented by the following general formula (1) described in “Studies in Inorganic Chemistry 6 Phosphorus (Third Edition)” (ELSEVIER) and Examples thereof include cyclic phosphazenes represented by the following general formula (2).

Here, in the general formulas (1) and (2), n is an integer of 0 to 15, preferably 1 to 10, and R is selected from an alkyl group, an allyl group, an alkoxy group, an allyloxy group, an amino group, and a hydroxy group. Any functional group is indicated. The alkoxy group and allyloxy group may be modified with an alkyl group, an allyl group, an amino group, a hydroxy group, or the like. The amino group may be modified with an alkyl group, an allyl group, or the like. Specific examples of the phosphazene compound used in the present invention include propoxyphosphazene, phenoxyphosphazene, methylphenoxyphosphazene, aminophosphazene, fluoroalkylphosphazene and the like. In particular, phenoxyphosphazene is preferable in view of its synthesis method and availability. These may be one kind or a mixture of two or more kinds, and may be a mixture of cyclic and linear. Further, in the phosphazene compound used in the present invention, all R in the same molecule may be the same functional group, or two or more different functional groups. Specific examples of such mixed substituted phosphazene compounds include phosphazene compounds in which a part of the molecule is substituted with a phenoxy group and then substituted with a propoxy group, that is, phenoxypropoxyphosphazene. Commercially available phosphazene compounds are generally synthesized by replacing chlorophosphazene with alcohol, phenol or the like.

The compounding quantity of a phosphazene compound (C) is 0.5-25 weight part with respect to a total of 100 weight part of (A) and (B). A blending amount of less than 0.5 parts by weight is not preferable because flame retardancy cannot be obtained. On the other hand, when the blending amount exceeds 25 parts by weight, the heat resistance (thermal deformability) and impact strength of the composition are remarkably lowered, which is not preferable. More preferably, it is in the range of 4 to 20 parts by weight, more preferably 8 to 15 parts by weight.

As the rubber-like elastic body (D) used in the present invention, a butadiene rubber-like elastic body having a core-shell structure or a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component cannot be separated. Examples thereof include a composite rubber graft copolymer obtained by graft-polymerizing one or two or more vinyl monomers to a composite rubber having a structure intertwined with each other.

As a butadiene rubber-like elastic body having a core / shell structure, a styrene-butadiene polymer or butadiene polymer is used for the core part, and a methyl methacrylate polymer or a styrene / methyl methacrylate copolymer is used for the shell part. Representative products include Rohm & Haas Paraloid EXL2602, Mitsubishi Rayon's Metabrene E-901, and the like.

In order to obtain the composite rubber-based graft copolymer used in the present invention, first, various cyclic organosiloxanes having three or more members, for example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane. Etc., and a latex of polyorganosiloxane rubber is prepared by emulsion polymerization using a crosslinking agent and / or a grafting agent, and then an alkyl (meth) acrylate monomer, a crosslinking agent and a grafting agent are added to the polyorganosiloxane rubber. It is obtained by impregnating with a latex and polymerizing. Examples of the alkyl (meth) acrylate monomer used herein include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and alkyls such as hexyl methacrylate and 2-ethylhexyl methacrylate. Although methacrylate is mentioned, it is particularly preferable to use n-butyl acrylate. Examples of vinyl monomers to be graft polymerized to the composite rubber include aromatic vinyl compounds such as styrene and α-methylstyrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, and methacrylic monomers such as methyl methacrylate and 2-ethylhexyl methacrylate. Examples thereof include acrylic acid esters such as acid ester, methyl acrylate, ethyl acrylate, and butyl acrylate, and these are used alone or in combination of two or more. The average particle size of the composite rubber is preferably 0.08 to 0.6 μm. When the average particle size of the composite rubber is less than 0.08 μm, the impact resistance of the resulting resin composition is lowered, and when the average particle size exceeds 0.6 μm, the surface appearance of the molded product of the resulting resin composition is deteriorated. There is a case. Particularly preferred is a product commercially available from Mitsubishi Rayon Co., Ltd. under the trade name Methbrene S-2001.

The compounding amount of the rubber-like elastic body (D) is 0 to 10 parts by weight, more preferably 0 to 7 parts by weight, more preferably 0 to 0 parts by weight with respect to 100 parts by weight as a total of (A) and (B). The range is 5 parts by weight. By adding the rubber-like elastic body (D) component, the impact strength of the composition is further improved.

As the fiber-forming fluorine-containing polymer (E) used in the present invention, one that forms a fibril-like structure in a resin is preferable. For example, polytetrafluoroethylene, a tetrafluoroethylene copolymer (for example, tetra Fluoroethylene / hexafluoropropylene copolymer, etc.), partially fluorinated polymers as shown in US Pat. No. 4,379,910, polycarbonates produced from fluorinated diphenols, and the like. In particular, polytetrafluoroethylene having a molecular weight of 1,000,000 or more and a fibril-forming ability having a secondary particle diameter of 100 μm or more is preferably used.
These are commercially available, for example, as NEOFRON FA500 from Daikin Industries, Ltd., and are available.

A polytetrafluoroethylene-containing mixed powder can be used as the fiber-forming fluorine-containing polymer (E). The polytetrafluoroethylene-containing mixed powder is composed of polytetrafluoroethylene particles having a particle diameter of 10 μm or less and an organic polymer, and the polytetrafluoroethylene has a particle diameter exceeding 10 μm and is not an aggregate. Are preferably used. Furthermore, from the viewpoint of dispersibility when blended in a resin, in a dispersion obtained by mixing an aqueous dispersion of polytetrafluoroethylene particles having a particle diameter of 0.05 to 1.0 μm and an aqueous dispersion of organic polymer particles, It is necessary to use a polymer obtained by polymerizing a vinyl monomer and then pulverizing it by coagulation or spray drying. The polytetrafluoroethylene-containing mixed powder used for obtaining the polytetrafluoroethylene-containing mixed powder according to the present invention is prepared by emulsion polymerization using a fluorine-containing surfactant. It is obtained by polymerizing monomers.

  Fluorine-containing olefins such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, and perfluoroalkyl vinyl ether as copolymerization components in the emulsion polymerization of polytetrafluoroethylene particles as long as the properties of polytetrafluoroethylene are not impaired. Fluorine-containing alkyl (meth) acrylates such as perfluoroalkyl (meth) acrylate can be used. The content of the copolymer component is preferably 10% by weight or less with respect to tetrafluoroethylene.

  Commercially available raw materials for polytetrafluoroethylene particle dispersions include: Fullon AD-1 and AD-936 manufactured by Asahi Glass Fluoropolymer, Polyflon D-1 and D-2 manufactured by Daikin Industries, Ltd., and Teflon manufactured by Mitsui DuPont Fluorochemical Co., Ltd. 30J etc. can be mentioned as a representative example.

  The organic polymer particle aqueous dispersion used for obtaining the polytetrafluoroethylene-containing mixed powder can be obtained by polymerizing a vinyl monomer by a known method such as emulsion polymerization.

  The vinyl monomer used to obtain the organic polymer particle aqueous dispersion, and the polytetrafluoroethylene particle aqueous dispersion having a particle diameter of 0.05 to 1.0 μm and the organic polymer particle aqueous dispersion were mixed. Although it does not restrict | limit especially as a vinyl monomer polymerized in a dispersion liquid, It is preferable that it is a thing with high affinity with resin from a dispersible viewpoint at the time of mix | blending with resin.

  Specific examples of these vinyl monomers include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, t-butylstyrene, o-ethylstyrene, p-chlorostyrene, o-chlorostyrene, 2, Aromatic vinyl monomers such as 4-dichlorostyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, Butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate, cyclohexane methacrylate (Meth) acrylic acid ester monomers such as xylyl; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; α, β-unsaturated carboxylic acids such as maleic anhydride; N-phenylmaleimide, N-methylmaleimide, Maleimide monomers such as N-cyclohexylmaleimide; Epoxy group-containing monomers such as glycidyl methacrylate; Vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; Vinyl carboxylates such as vinyl acetate and vinyl butyrate Body; α-olefin monomers such as ethylene, propylene, and isobutylene; and diene monomers such as butadiene, isoprene, and dimethylbutadiene. These monomers can be used alone or in admixture of two or more.

  Among these monomers, 30 or more monomers selected from the group consisting of aromatic vinyl monomers and vinyl cyanide monomers are preferred from the viewpoint of affinity with the resin. Mention may be made of monomers containing at least% by weight. Particularly preferred is a monomer containing 30% by weight or more of one or more monomers selected from the group consisting of styrene and acrylonitrile.

  The polytetrafluoroethylene content in the polytetrafluoroethylene-containing mixed powder is preferably 0.1 to 90% by weight. If it is less than 0.1% by weight, the flame retardancy improving effect may be insufficient, and if it exceeds 90% by weight, the surface appearance may be adversely affected.

  The mixed powder containing polytetrafluoroethylene is poured into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved and dried after salting out, solidifying, or by spray drying. Can be used.

  In contrast to the usual polytetrafluoroethylene fine powder, it is difficult to uniformly disperse in the resin because it becomes an aggregate of 100 μm or more in the step of recovering as a powder from the state of the particle dispersion. The polytetrafluoroethylene-containing mixed powder used in the present invention is extremely excellent in dispersibility with respect to the resin because polytetrafluoroethylene alone does not form a domain having a particle diameter exceeding 10 μm. As a result, in the polycarbonate resin composition of the present invention, polytetrafluoroethylene is efficiently made into fine fibers in the resin composition, and the flame retardancy is excellent, and the surface property and impact property are also excellent.

  The compounding amount of the fiber-forming fluoropolymer (E) is 0.01 to 2 parts by weight with respect to 100 parts by weight as a total of (A) and (B). If the blending amount is less than 0.01 parts by weight, the anti-dripping property is inferior, and if it exceeds 2 parts by weight, the surface appearance and mechanical properties (impact strength) deteriorate, which is not preferable. More preferably, it is in the range of 0.2 to 1 part by weight.

Examples of the acid scavenger (F) used in the present invention include epoxy stabilizers listed below. When such an epoxy stabilizer is contained, the heat-and-moisture resistance (hydrolysis resistance) of the resin composition can be improved.

Examples of the epoxy stabilizer include epoxidized soybean oil, epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxy 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, 4 -(3,4-epoxy-5-methylcyclohexyl) butyl-3 ', 4'-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl-3,4-epoxycyclohexylca Boxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6′-methylsiloxycarboxylate, bisphenol A diglycidyl ether, tetrabromobisphenol A glycidyl ether, diglycidyl ester of phthalic acid, diglycidyl of hexahydrophthalic acid Esters, bis-epoxy dicyclopentadienyl ether, bis-epoxy ethylene glycol, bis-epoxy cyclohexyl adipate, butadiene diepoxide, tetraphenylethylene epoxide, octyl epoxy tartrate, epoxidized polybutadiene, 3,4-dimethyl-1, 2-epoxycyclohexane, 3,5-dimethyl-1,2-epoxycyclohexane, 3-methyl-5-tert-butyl-1,2-epoxycyclohexane, octadec 2,2-dimethyl-3,4-epoxycyclohexyl carboxylate, N-butyl-2,2-dimethyl-3,4-epoxycyclohexyl carboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexyl carboxylate N-butyl-2-isopropyl-3,4-epoxy-5-methylcyclohexyl carboxylate, octadecyl-3,4-epoxycyclohexyl carboxylate, 2-ethylhexyl-3 ′, 4′-epoxycyclohexyl carboxylate, 4, 6-dimethyl-2,3-epoxycyclohexyl-3 ′, 4′-epoxycyclohexylcarboxylate, 4,5-epoxytetrahydrophthalic anhydride, 3-tert-butyl-4,5-epoxytetrahydrophthalic anhydride, diethyl- 4,5-d Poxy-cis-1,2-cyclohexyl dicarboxylate, di-n-butyl-3-t-butyl-4,5-epoxy-cis-1,2-cyclohexyl dicarboxylate and the like can be mentioned.

Of these, epoxy soybean oil and alicyclic epoxy resins are preferably used. The latter is particularly preferably 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate or bis- (3,4-epoxycyclohexyl) adipate. These epoxy stabilizers are available as O-130P, R-51 manufactured by Asahi Denka Kogyo Co., Ltd., Celoxide 2021P manufactured by Daicel Chemical Industries, Ltd., or Celoxide 2080.

The compounding quantity of an acid scavenger (F) is the range of 0.01-2 weight part with respect to a total of 100 weight part of (A) and (B). If the blending amount is less than 0.01 parts by weight, sufficient wet heat deterioration characteristics cannot be obtained. Conversely, if the blending amount exceeds 2 parts by weight, mold contamination due to exudation from the resin composition or impact of the composition. This is not preferable because the strength is lowered. The amount is more preferably 0.050.6 parts by weight, still more preferably 0.1 to 0.3 parts by weight.

The mold release agent (G) used in the present invention is not particularly limited as long as it exhibits a mold release effect, but polyolefin wax, glycerol monostearate, glycerol tristearate, pentaerythritol tetrastearate, Examples thereof include beeswax, montanic acid ester wax, carboxylic acid ester (eg, stearyl stearate) and the like, and these may be used alone or in combination of two or more.

  The compounding quantity of a mold release agent (G) is the range of 0.01-3 weight part with respect to a total of 100 weight part of (A) and (B). If the blending amount is less than 0.01 parts by weight, the releasability is not sufficient. Conversely, if the blending amount exceeds 3 parts by weight, the resin may be exuded by the mold release agent (G) during bleeding or molding. This is not preferable because defects such as mold contamination occur. Preferably, it is 0.05-2 weight part, More preferably, it is the range of 0.2-1 weight part.

  There are no particular restrictions on the method of blending the various components (A), (B), (C), (D), (E), (F) and (G) of the present invention. For example, a method of blending all the components at once. Alternatively, a method of blending the remaining components in a premixed component (A) or (B) can be performed freely.

  The method of blending them is not particularly limited, and they can be mixed with an optional mixer such as a tumbler, ribbon blender, high speed mixer, etc., and can be easily melt-kneaded with an ordinary single screw or twin screw extruder.

  Further, various heat stabilizers, antioxidants, fluorescent brighteners, pigments / dyes, fillers, softeners, antistatic agents, and the like in the polycarbonate resin composition of the present invention within a range not impairing the effects of the present invention. You may mix | blend additives and other polymers, such as a ultraviolet absorber, spreading agents (liquid paraffin etc.), a silicone type flame retardant, and an organic metal salt.

Examples of the organic metal salt compound include aromatic sulfonic acid metal salts and perfluoroalkanesulfonic acid metal salts. Examples of the metal include alkali metals and alkaline earth metals. Preferably, potassium salt of 4-methyl-N- (4-methylphenyl) sulfonyl-benzenesulfonamide, potassium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-3'-disulfonate, paratoluenesulfonic acid Sodium, perfluorobutanesulfonic acid potassium salt and the like can be used.

  Examples of the filler include glass fiber, glass bead, glass flake, carbon fiber, talc powder, clay powder, mica, aluminum borate whisker, potassium titanate whisker, wollastonite powder, silica powder, and alumina powder.

Examples of the other polymer include polyesters such as polyethylene terephthalate and polybutylene terephthalate, polypropylene, polyethylene, and various thermoplastic elastomers.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. “Parts” are based on weight unless otherwise specified.

1. Polycarbonate resin:
Caliber 200-13, manufactured by Sumitomo Dow
(Viscosity average molecular weight: 21000, hereinafter abbreviated as “PC”)
2. ABS resin: Santac AT07 (bulk polymerized ABS resin) manufactured by Japan A & L
(Hereinafter abbreviated as “ABS”)
3. Phosphazene compounds:
CP-134H manufactured by Phenoxyphosphazene Chemipro Kasei Co., Ltd.
(Hereinafter abbreviated as “PZ”)

4). Rubber elastic body:
1. Rohm and Haas Paraloid EXL2602
(Hereinafter abbreviated as “D-1”)
2. Mitsubishi Rayon's Metabrene S-2001
(Hereinafter abbreviated as “D-2”)
5. Fiber-forming fluorine-containing polymer:
1. PTFE resin Neoflon FA500 manufactured by Daikin Industries
(Hereinafter abbreviated as “PTFE”)
2. Polytetrafluoroethylene-containing mixed powder Metablene A3800 manufactured by Mitsubishi Rayon Co., Ltd.
PTFE resin content: 50% (hereinafter abbreviated as “PTFE-MB”)
6). Acid scavenger:
Asahi Denka Kogyo Co., Ltd. Epoxidized soybean oil Adeka Sizer O-130P
(Hereinafter abbreviated as “stabilizer”)
7). Release agent:
Montanic acid ester wax / Lico wax E manufactured by Clariant Japan
(Hereinafter abbreviated as “MR”)

  After blending based on the blending ratio of each component shown in Tables 2 and 3, it was dry blended and granulated using a 37 mm twin screw extruder (KTX37 manufactured by Kobe Steel) under the condition of a melting temperature of 240 ° C. . Each test piece was created from the obtained pellets under the condition of a cylinder set temperature of 260 ° C. by an injection molding machine (J100EC5 manufactured by Nippon Steel), and the following evaluations were performed. The evaluation results are shown in Table 1.

1. Flame retardance:
A 1.6mm-thick specimen is left for 48 hours in a temperature-controlled room with a temperature of 23 ° C and a humidity of 50%, and conforms to UL94 test (flammability test of plastic materials for equipment parts) established by Underwriters Laboratories. The flame retardancy was evaluated. UL94V is a method of evaluating flame retardance from the afterflame time and drip properties after indirect flames of a burner for 10 seconds on a test piece of a predetermined size held vertically, and is divided into the following classes: .

上に示す残炎時間とは、着火源を遠ざけた後の試験片が有炎燃焼を続ける時間の長さであり、ドリップによる綿の着火とは、試験片の下端から約３００ｍｍ下にある標識用の綿が、試験片からの滴下（ドリップ）物によって着火するかどうかによって決定される。
評価の基準は、１．６ｍｍ厚さの試験においてＶ−０を合格とした。

The after-flame time shown above is the length of time that the specimen keeps flaming combustion after moving the ignition source away, and the ignition of cotton by drip is about 300 mm below the lower end of the specimen. It is determined by whether the marking cotton is ignited by a drip from the specimen.
As a standard for evaluation, V-0 was accepted in the 1.6 mm thickness test.

2. Impact resistance:
The notched Izod impact strength was measured according to ASTM D-256, and an impact value of 20 kg · cm / cm or more was regarded as acceptable. The thickness is 3.2 mm.

3. Deflection temperature under load:
The deflection temperature under load (test piece thickness: 6.4 mm) was measured according to ASTM D648. 75 degreeC or more was set as the pass.

4). Surface appearance:
The surface appearance of the 70 × 55 × 3 mm color chip was visually confirmed.
Very good (◎) and good (○) were accepted and bad (x) were rejected.

5. 3. Resistance to heat and humidity deterioration under pressure conditions of 120 ° C. and 100% relative humidity using a pressure cooker (TPC-411 manufactured by Tabai Espec). The color chip was exposed for 48 hours. And polycarbonate resin was fractionated from the test piece before and behind exposure, and the molecular weight was measured by the solution viscosity method using a methylene chloride. (Viscosity tube is Cannon Fenceke viscosity tube, measurement temperature is 25 ° C)
The polycarbonate molecular weight of the test piece after the vapor exposure test was determined to be 13,000 or more.

6). Release property Size: 70mm (length) x 150mm (width) x 40mm (height) box-shaped test piece is injection-molded, and the mold release property at the time of release is visually and auditorily (size of squeak noise). Confirmed.
Very good (◎) and good (○) were accepted and bad (x) were rejected.

＊１．分子量の値：×１０００

* 1. Molecular weight value: x1000

＊１．分子量値（耐湿熱劣化性）：×１０００
注１．難燃性がＮＲとはどのクラスの難燃性にも属さないことを表す。

* 1. Molecular weight value (moisture and heat resistance): x1000
Note 1. The flame retardancy is NR, which means that it does not belong to any class of flame retardancy.

As shown in Examples 1 to 8, flame retardant, Izod impact strength, deflection temperature under load, surface appearance, mold release, for the essential components of the present invention and those satisfying the specified range of the blending amount of each blending component Standards were satisfied with respect to all performance such as heat resistance and heat and heat resistance.
On the other hand, as shown in Comparative Examples 1 to 5, those in which the blending amount of the essential components of the present invention did not satisfy the specified value range had respective defects.
Comparative Example 1
This was a case where the blending amount of the phosphazene compound was further smaller than the lower limit of the specified range, and the flame retardancy was rejected.
Comparative Example 2
This was a case where the blending amount of the phosphazene compound exceeded the upper limit of the specified range, and the impact strength and the weighted deflection temperature were rejected.
Comparative Example 3
This was a case where the blending amount of the fiber-forming fluoropolymer was smaller than the lower limit of the specified range, and the flame retardancy was rejected.
Comparative Example 4
This was a case where the amount of the acid scavenger was further less than the lower limit of the specified range, and the wet heat deterioration was rejected.
Comparative Example 5
This is a case where the compounding amount of the release agent is further smaller than the lower limit of the specified range, and the release property was rejected.

Claims (7)

For a total of 100 parts by weight of polycarbonate resin (A) 1 to 99% by weight and rubber-reinforced styrene resin (B) 99 to 1% by weight, 0.5 to 25 parts by weight of phosphazene compound (C), rubber-like elastic body ( D) 0-10 parts by weight, fiber-forming fluoropolymer (E) 0.01-2 parts by weight, acid scavenger (F) 0.01-2 parts by weight, and release agent (G) 0.01-3 A flame-retardant polycarbonate-based resin composition, comprising: parts by weight. The flame retardant polycarbonate resin composition according to claim 1, wherein the phosphazene (C) is phenoxyphosphazene. A structure in which the rubber-like elastic body (D) is entangled with each other so that the butadiene rubber-like elastic body having a core-shell structure and / or the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber-like elastic body cannot be separated. The flame-retardant polycarbonate resin composition according to claim 1, which is a composite rubber-based graft copolymer obtained by graft-polymerizing one or two or more vinyl monomers to a composite rubber containing The flame-retardant polycarbonate resin composition according to claim 1, wherein the fiber-forming fluoropolymer (E) is polytetrafluoroethylene and / or a mixed powder containing polytetrafluoroethylene. The flame retardant polycarbonate resin composition according to claim 1, wherein the acid scavenger (F) is an epoxy stabilizer. The mold release agent (G) is one or more compounds selected from glycerol monostearate, pentaerythritol tetrastearate, glycerol tristearate, polyolefin wax, beeswax, montanate wax, carboxylic acid ester The flame-retardant polycarbonate resin composition according to claim 1. A molded article formed by molding the flame-retardant polycarbonate resin composition according to any one of claims 1 to 7.